US9382417B2 - Process for the preparation of polyether carbonate polyols - Google Patents
Process for the preparation of polyether carbonate polyols Download PDFInfo
- Publication number
- US9382417B2 US9382417B2 US13/636,509 US201113636509A US9382417B2 US 9382417 B2 US9382417 B2 US 9382417B2 US 201113636509 A US201113636509 A US 201113636509A US 9382417 B2 US9382417 B2 US 9382417B2
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- US
- United States
- Prior art keywords
- activation
- employed
- additive
- alkylene oxides
- functional starter
- Prior art date
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- -1 carbonate polyols Chemical class 0.000 title claims abstract description 209
- 229920005862 polyol Polymers 0.000 title claims abstract description 172
- 229920000570 polyether Polymers 0.000 title claims abstract description 166
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 165
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 92
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 182
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 144
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 139
- 239000007858 starting material Substances 0.000 claims abstract description 113
- 239000000654 additive Substances 0.000 claims abstract description 111
- 229910052751 metal Inorganic materials 0.000 claims abstract description 107
- 239000002184 metal Substances 0.000 claims abstract description 107
- 150000003839 salts Chemical class 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 239000000126 substance Substances 0.000 claims abstract description 82
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 62
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 25
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims abstract description 13
- 150000002989 phenols Chemical class 0.000 claims abstract description 10
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 claims abstract description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 7
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical class [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims abstract 2
- 230000004913 activation Effects 0.000 claims description 94
- 230000000996 additive effect Effects 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000007792 addition Methods 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 28
- 230000000536 complexating effect Effects 0.000 claims description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 20
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 20
- 150000001298 alcohols Chemical class 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000003446 ligand Substances 0.000 claims description 18
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 17
- 239000008116 calcium stearate Substances 0.000 claims description 17
- 235000013539 calcium stearate Nutrition 0.000 claims description 17
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 15
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- SZAVHWMCBDFDCM-KTTJZPQESA-N cobalt-60(3+);hexacyanide Chemical compound [60Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] SZAVHWMCBDFDCM-KTTJZPQESA-N 0.000 claims description 9
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- 150000003573 thiols Chemical class 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 claims description 4
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 claims description 3
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 229940078456 calcium stearate Drugs 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 229940057948 magnesium stearate Drugs 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- YMXDOZWKTUBYLU-UHFFFAOYSA-N 1-nitroethenylbenzene Chemical compound [O-][N+](=O)C(=C)C1=CC=CC=C1 YMXDOZWKTUBYLU-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- GICQWELXXKHZIN-UHFFFAOYSA-N 2-[2-[(2-methylpropan-2-yl)oxy]ethoxy]ethanol Chemical compound CC(C)(C)OCCOCCO GICQWELXXKHZIN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 2
- 235000019960 monoglycerides of fatty acid Nutrition 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
- YJUIKPXYIJCUQP-UHFFFAOYSA-N trizinc;iron(3+);dodecacyanide Chemical compound [Fe+3].[Fe+3].[Zn+2].[Zn+2].[Zn+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YJUIKPXYIJCUQP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000004897 thiazines Chemical class 0.000 abstract description 4
- 150000003557 thiazoles Chemical class 0.000 abstract description 4
- 150000004893 oxazines Chemical class 0.000 abstract description 3
- 150000002991 phenoxazines Chemical class 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 73
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 32
- 150000005676 cyclic carbonates Chemical class 0.000 description 30
- 239000011777 magnesium Substances 0.000 description 30
- 239000007787 solid Substances 0.000 description 30
- 239000006227 byproduct Substances 0.000 description 29
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 28
- 150000007942 carboxylates Chemical class 0.000 description 20
- 150000002825 nitriles Chemical class 0.000 description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 17
- 150000002118 epoxides Chemical class 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 229950000688 phenothiazine Drugs 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 150000004820 halides Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 150000002540 isothiocyanates Chemical class 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
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- 238000005119 centrifugation Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
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- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 4
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- 229910017052 cobalt Inorganic materials 0.000 description 4
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- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FRBUISUEBZDLGA-UHFFFAOYSA-N CC.CC.OC1=C(O)C2=CC=CC=C2C=C1.OC1=C(O)C=CC=C1 Chemical compound CC.CC.OC1=C(O)C2=CC=CC=C2C=C1.OC1=C(O)C=CC=C1 FRBUISUEBZDLGA-UHFFFAOYSA-N 0.000 description 3
- RPHYLOMQFAGWCD-UHFFFAOYSA-N CC.OC1=CC=CC=C1 Chemical compound CC.OC1=CC=CC=C1 RPHYLOMQFAGWCD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002266 Pluriol® Polymers 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
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- ODADONMDNZJQMW-UHFFFAOYSA-N diethoxy-ethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](CC)(OCC)CCCOCC1CO1 ODADONMDNZJQMW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Chemical class 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Chemical class OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- 229960002743 glutamine Drugs 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical class CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Chemical class OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Chemical class CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-M linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O DTOSIQBPPRVQHS-PDBXOOCHSA-M 0.000 description 1
- 229940040452 linolenate Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229960003646 lysine Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229930182817 methionine Chemical class 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Chemical class OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920001446 poly(acrylic acid-co-maleic acid) Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- 229960004441 tyrosine Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Chemical class OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 239000004474 valine Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
Definitions
- the present invention relates to a process for the preparation of polyether carbonate polyols by catalytic copolymerization of carbon dioxide (CO 2 ) with alkylene oxides in the presence of one or more H-functional starter substances with the aid of double metal cyanide (DMC) catalysts and in the presence of additives.
- CO 2 carbon dioxide
- DMC double metal cyanide
- R represents an organic radical, such as alkyl, alkylaryl or aryl, each of which can also contain hetero atoms, such as, for example, O, S, Si etc., and wherein e and f represent an integer
- the product shown here for the polyether carbonate polyol in equation (I) is merely to be understood as meaning that blocks with the structure shown can in principle be found in the polyether carbonate polyol obtained, but the sequence, number and length of the blocks and the OH functionality of the starter can vary and is not limited to the polyether carbonate polyol shown in equation (I).
- U.S. Pat. No. 4,500,704 describes the use of DMC catalysts for the copolymerization of epoxides and carbon dioxide.
- the DMC catalyst is prepared in an aqueous medium and therefore contains a large amount of water.
- the water is removed down to an amount of less than 5 wt. %.
- organic complexing agents or coordination compounds such as alcohols, ethers, esters, sulfides, ketones, aldehydes, amides and/or nitriles.
- DMC catalysts are prepared in the presence of these compounds, these are said to make up 5-30 wt. % of the total weight of the catalyst.
- U.S. Pat. No. 4,500,704 does not disclose that such compounds can be employed as additives in the copolymerization of epoxides with carbon dioxide.
- WO-A 2004/087788 describes the preparation of polyether carbonate polyols of narrow polydispersity using DMC catalysts, which is achieved by adding a sterically hindered chain transfer reagent which is capable of protonating the growing polymer chain.
- Sterically hindered chain transfer reagents which are mentioned are: sterically hindered alcohols (e.g.
- tert-butanol or substituted tert-butanols tertiary aliphatic alcohols
- sterically hindered phenols e.g. di-tert-butylphenol or substituted di-tert-butylphenols
- sterically hindered, polysubstituted phenols and sterically hindered benzoic acid derivatives e.g. di-tert-butylbenzoic acid or substituted di-tert-butylbenzoic acids.
- the sterically hindered chain transfer reagents can be added at the start of the reaction or during the polymerization, preferably in at least a 10-fold molar excess relative to the DMC catalyst.
- Example 1 In Example 1, 6 mmol of tert-butanol and 0.026 mmol of Zn were employed in the catalyst, from which a ratio of additive/catalyst of 230 results. The number of Zn centres in one mole of DMC catalyst is not disclosed. The large amount of sterically hindered chain transfer reagent added relative to the amount of the DMC catalyst is a disadvantage.
- step ( ⁇ ) wherein the additive A) is added in step ( ⁇ ) to the H-functional starter substance or the mixture of at least two H-functional starter substances, optionally before or after the drying, and/or the additive A) is added in step ( ⁇ ) to the part amount of one or more alkylene oxides to the mixture resulting from step ( ⁇ ), and
- additive A) is at least one compound chosen from the group consisting of sterically non-hindered phenols, catechols, pyrocatechols, thiazines, phenothiazines, thiazoles, benzothiazoles, oxazines, phenoxazines, 2,2,6,6-tetramethylpiperidine 1-oxyl and nitrostyrenes.
- a part amount of alkylene oxide compound is added to the DMC catalyst, a temperature peak (“hot spot”) and/or a drop in pressure in the reactor being observed due to a subsequent exothermic chemical reaction.
- the part amount of alkylene oxide compound can also contain one or more additives A), and the DMC catalyst can be mixed with one or more additives A) and optionally with one or more metal salts.
- the process step of activation is the time span from the addition of the part amount of alkylene oxide compound, optionally in the presence of CO 2 , to the DMC catalyst up to the hot spot.
- a step for drying the DMC catalyst, optionally one or more of the additives A) and optionally one or more metal salts and optionally the starter by elevated temperature and/or reduced pressure can precede the activation step, this step of drying not being part of the activation step in the context of the present invention.
- Possible additives A) are, preferably, sterically non-hindered phenols (A-1) according to formula (II)
- the substituent or substituents R i are arranged in the ortho position relative to the hydroxyl group.
- the sterically non-hindered phenols are 4-dinitrophenol and/or 2,4-dinitrophenol.
- Possible additives A) are also, preferably, catechols according to formula (Ma) and pyrocatechols according to formula (IIIb)
- Possible additives A) are also, preferably, thiazines according to formula (IVa) and phenothiazines according to formula (IVb)
- Possible additives A) are also, preferably, thiazoles according to formula (Va) and benzothiazoles according to formula (Vb)
- Possible additives A) are also, preferably, oxazines according to formula (VIa) and phenoxazines according to formula (VIb)
- Possible additives A) are also nitrostyrenes, such as, for example, ⁇ -nitrostyrene or ⁇ -nitrostyrene, particularly preferably trans- ⁇ -nitrostyrene.
- step ( ⁇ ) wherein the additive A) is added in step ( ⁇ ) to the H-functional starter substance or the mixture of at least two H-functional starter substances, optionally before or after the drying, and/or the additive A) is added in step ( ⁇ ) to the part amount of one or more alkylene oxides to the mixture resulting from step ( ⁇ ),
- metal salt B) is added in step ( ⁇ ) to the H-functional starter substance or the mixture of at least two H-functional starter substances before or after the drying (optionally together with the additive A),
- alkaline earth metal halides such as, for example, magnesium chloride
- alkaline earth metal carboxylates such as, for example, magnesium acetate, calcium acetate, magnesium stearate, calcium stearate
- aluminium carboxylates such as, for example, aluminium stearate
- Alkaline earth metals in the context of the invention are the elements of group 2 of the periodic table of the elements and include the elements beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
- Halides are the anions of the elements of group 17 of the periodic table of the elements and include the anions fluoride, chloride, bromide, iodide and astatine.
- Carboxylates in the context of this invention are anions of carboxylic acids which contain at least one carboxylate group.
- the carboxylates contain, for example, only one carboxylate group according to formula (VII) R 1 —COO ⁇ (VII) wherein R 1 represents H, C 1 to C 30 -alkyl (such as, for example, CH 3 , CH 3 —CH 2 , CH 3 —CH 2 —CH 2 , CH 3 —(CH 2 ) 3 , CH 3 —(CH 2 ) 4 , CH 3 —(CH 2 ) 5 , CH 3 —(CH 2 ) 6 , CH 3 —(CH 2 ) 7 , CH 3 —(CH 2 ) 8 , CH 3 —(CH 2 ) 14 , CH 3 —(CH 2 ) 16 and branched isomers thereof), C 7 to C 30 -alkaryl (such as, for example, benzyl) or C 6 to C 30 -aryl (such as, for example, phenyl or naphthyl).
- R 1 represents H, C 1 to C 30 -alkyl (
- the carboxylates can similarly be unsaturated carboxylates, such as, for example, acrylate, methacrylate and unsaturated fatty acid salts, such as oleate (salt of oleic acid), where R 1 ⁇ CH 3 —(CH 2 ) 7 —CH ⁇ CH—(CH 2 ) 7 , linolate (salt of linoleic acid), where R 1 ⁇ CH 3 —(CH 2 ) 4 —CH ⁇ CH—CH 2 —CH ⁇ CH—(CH 2 ) 7 , and linolenate (salt of linolenic acid), where R 1 ⁇ CH 3 —CH 2 —CH ⁇ CH—CH 2 —CH ⁇ CH—CH 2 —CH ⁇ CH—(CH 2 ) 7 .
- unsaturated carboxylates such as, for example, acrylate, methacrylate and unsaturated fatty acid salts, such as oleate (salt of oleic acid), where R 1 ⁇
- R 1 in formula (II) can also be heteroaromatic, such as, for example, in the case of nicotinoate.
- the carboxylates can also contain, for example, two carboxylate groups according to formula (VIII) ⁇ OOC—R 2 —COO ⁇ (VIII) wherein R 2 represents a single bond (in the case of oxalate), C 1 to C 30 -alkylene (such as, for example, CH 2 , CH 2 —CH 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 5 , (CH 2 ) 6 , (CH 2 ) 7 , —CH ⁇ CH— (in the case of maleate or fumarate)), C 7 to C 30 -alkaryl (such as, for example, benzyl) or C 6 to C 30 -aryl (such as, for example, phenyl or naphthyl).
- R 2 represents a single bond (in the case of oxalate)
- C 1 to C 30 -alkylene such as, for example, CH 2 , CH 2 —CH 2 , (CH 2 )
- the carboxylates can moreover also be substituted by hetero atoms (such as, for example, halogens, such as fluorine, chlorine, bromine, iodine) and/or by one or more functional groups, such as hydroxyl (—OH), amine (primary amino group —NH 2 , secondary amino group —NH or tertiary amino group —N) or thiol (—SH).
- hetero atoms such as, for example, halogens, such as fluorine, chlorine, bromine, iodine
- one or more functional groups such as hydroxyl (—OH), amine (primary amino group —NH 2 , secondary amino group —NH or tertiary amino group —N) or thiol (—SH).
- hydroxycarboxylic acids such as glycollate (salt of glycollic acid), lactate (salt of lactic acid), tartrate (salt of tartaric acid), salicylate (salt of salicylic acid).
- salts of amino acids such as the salts of alanine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine.
- salts of carboxylic acids with a thiol group such as, for example, the salts of 2-mercaptopropionic acid.
- carboxylates with two functional groups are the salts of cysteine (containing an amino group and a thiol group).
- sterically non-hindered phenols such as, for example, 4-nitrophenol and/or 2,4-dinitrophenol are employed as the additive A
- alkaline earth metal carboxylates such as, for example, magnesium acetate, calcium acetate, magnesium stearate, calcium stearate
- aluminium carboxylates such as, for example, aluminium stearate
- 2,4-dinitrophenol and/or 4-nitrophenol is employed as the additive A) and calcium stearate and/or aluminium stearate is employed as the metal salt B).
- the amount stated for the additives A) and optionally the metal salts B) employed is based on the ratio of the substance amount of the additive A) and, respectively, the metal salt B) employed (or the sum of the particular substance amounts employed) with respect to the substance amount of cobalt employed originating from the DMC catalyst (stated as [mmol of additive A]/[mmol of Co]) or [mmol of metal salt B]/[mmol of Co]).
- the additives A) can be employed in a total amount of from 0.2 to 10.0 [mmol of additive A)]/[mmol of Co].
- the additives A) are employed in a total amount of from 0.8 to 4.0 [mmol of additive A)]/[mmol of Co], particularly preferably in a total amount of from 1.2 to 3.0 [mmol of additive A)]/[mmol of Co].
- the metal salts B) can each be employed in a total amount of from 0.0 to 10.0 [mmol of metal salt B)]/[mmol of Co].
- the metal salts B) are employed in a total amount of from 0.8 to 4.0 [mmol of metal salt B)]/[mmol of Co], particularly preferably in a total amount of from 1.2 to 3.0 [mmol of metal salt B)]/[mmol of Co].
- the H-functional starter substance or a mixture of at least two H-functional starter substances is initially introduced into the reaction vessel and, where appropriate, water and/or other readily volatile compounds are removed. This is carried out, for example, by stripping by means of nitrogen (optionally under reduced pressure) or by distillation in vacuo at temperatures of from 50 to 200° C., preferably 80 to 160° C., particularly preferably at 100 to 140° C. This pretreatment of the starter substance or mixture of starter substances is called drying in the following for simplification.
- the DMC catalyst and one or more additives A) and optionally one or more metal salts B) can be already initially introduced into the reaction vessel in the H-functional starter substance or the mixture of at least two H-functional starter substances, but it is also possible for one or more additives A) and optionally the optionally dried metal salt B) to be added to the DMC catalyst, which has then been dried, only after drying of the H-functional starter substance or the mixture of H-functional starter substances.
- the DMC catalyst can be added in the solid form or as a suspension in an H-functional starter substance. If the catalyst is added as a suspension, this is preferably added before drying of the H-functional starter substance(s).
- the activation ( ⁇ ) is carried out by a procedure in which
- the additive A) prefferably be dissolved in the particular part amount of one or more alkylene oxides which is employed in steps ( ⁇ 1) to ( ⁇ 4) and to be added to the process.
- the particular part amount of one or more alkylene oxides which is employed in the activation in steps ⁇ 1 to ⁇ 4 is 2.0 to 15.0 wt. %, preferably 2.5 to 14.0 wt. %, particularly preferably 3.0 to 13.0 wt. % (based on the total amount of the amount of alkylene oxides employed in the activation and copolymerization).
- the metering of one or more alkylene oxides and optionally of the carbon dioxide is carried out after the drying of a starter substance or the mixture of several starter substances and the addition of the DMC catalyst and/or of the additive A) and optionally of the metal salt B), which is added as a solid or, in the case of the DMC catalyst in the form of a suspension, before or after the drying of the starter substance. If the DMC catalyst and/or the additive A) and optionally the metal salt B) is added after the drying of the starter substance, this DMC catalyst and/or the metal salt B) should preferably be dried, for example in a process analogous to the drying of the starter substance.
- the metering of one or more alkylene oxides and of the carbon dioxide can in principle be carried out in various ways.
- the start of the metering can take place from a vacuum or under a previously selected prepressure.
- the prepressure is preferably established by passing in an inert gas, such as, for example, nitrogen, the pressure (absolute) being established at between 10 mbar to 10 bar, preferably 100 mbar to 8 bar and preferably 500 mbar to 6 bar.
- the mixture of one or more starter compounds and the DMC catalyst resulting from step ( ⁇ ) is charged, at a temperature of from 100° C.
- an inert gas nitrogen or a noble gas, such as, for example, argon
- a reduced pressure absolute
- the metering of one or more alkylene oxides and of the carbon dioxide can be carried out simultaneously or sequentially, it being possible for the total amount of carbon dioxide to be added all at once or by metering over the reaction time.
- the carbon dioxide is metered.
- the metering of one or more alkylene oxides is carried out simultaneously with or sequentially to the carbon dioxide metering. If several alkylene oxides are employed for synthesis of the polyether carbonate polyols, metering thereof can be carried out simultaneously or sequentially via in each case separate metering operations (additions), or via one or more metering operations, at least two alkylene oxides being metered as a mixture.
- the concentration of free alkylene oxides during the reaction in the reaction mixture is preferably >0 to 40 wt. %, particularly preferably >0-25 wt. %, most preferably >0-15 wt. % (in each case based on the weight of the reaction mixture).
- an excess of carbon dioxide based on the calculated amount of carbon dioxide incorporated in the polyether carbonate polyol, is employed, since due to the slowness of carbon dioxide to react an excess of carbon dioxide is advantageous.
- the amount of carbon dioxide can be determined via the overall pressure under the particular reaction conditions. The range of from 1 to 120 bar, preferably 50 to 110 bar, particularly preferably from 70 to 100 bar has proved to be advantageous as the overall pressure (absolute) for the copolymerization for the preparation of the polyether carbonate polyols.
- the copolymerization for the preparation of the polyether carbonate polyols is advantageously carried out at 50 to 150° C., preferably at 60 to 145° C., particularly preferably at 70 to 140° C. and very particularly preferably at 110 to 120° C. If temperatures below 50° C. are established, the reaction ceases. At temperatures above 150° C. the amount of undesirable by-products increases greatly. It is furthermore to be ensured that under the choice of pressure and temperature CO 2 passes from the gaseous state as far as possible into the liquid and/or supercritical liquid state. However, CO 2 can also be added to the reactor as a solid and can then pass into the liquid and/or supercritical liquid state under the reaction conditions chosen.
- Particularly preferred reactors are: tube reactor, stirred tank and loop reactor.
- Polyether carbonate polyols can be prepared in a stirred tank, it being possible for the stirred tank to be cooled via the reactor jacket, internal cooling surfaces and/or cooling surfaces in a pumped circulation, depending on the embodiment and mode of operation.
- the content of free epoxide in the reaction mixture of the stirred tank should not exceed 15 wt. % (see, for example, WO-A 2004/081082; page 3; line 14). Both in the semi-batch procedure, where the product is removed only after the end of the reaction, and in the continuous procedure, where the product is removed continuously, attention is therefore to be paid in particular to the metering rate of the epoxide.
- the epoxide reacts sufficiently rapidly. It is possible to feed in the carbon dioxide continuously or discontinuously. This depends on whether the epoxide is consumed rapidly enough and whether the product is optionally to contain CO 2 -free polyether blocks.
- the amount of carbon dioxide (stated as the pressure) can equally be varied during the addition of the epoxide. It is possible gradually to increase or to lower or to leave constant the CO 2 pressure during the addition of the epoxide.
- a further possible embodiment in the stirred tank for the copolymerization is characterized in that one or more H-functional starter compounds are metered continuously into the reactor during the reaction, where the additive A) employed and the metal salt B) optionally employed can be fed to the process together with the starter or are already initially introduced completely into the reaction vessel at the start of the reaction.
- the amount of H-functional starter compounds which are metered continuously into the reactor during the reaction is preferably at least 20 equivalent mol %, particularly preferably 70 to 95 equivalent mol % (in each case based on the total amount of H-functional starter compounds) (continuous addition of starter; CAOS process). However, it is not necessary to add the starter in portions. It can also already be initially introduced completely into the reaction vessel at the start of the reaction.
- the activated catalyst/starter mixture can be (further) copolymerized with epoxide and carbon dioxide in the stirred tank, but also in another reaction container (tube reactor or loop reactor).
- the activated catalyst and starter and the epoxide and carbon dioxide are pumped continuously through a tube.
- the molar ratios of the reaction partners vary according to the desired polymer.
- carbon dioxide is metered in here in its supercritical form, that is to say virtually liquid form, in order to render possible a better miscibility of the components.
- mixing elements are installed for better thorough mixing of the reaction partners, such as are marketed, for example, by Ehrfeld Mikrotechnik BTS GmbH, or mixer-heat exchanger elements which simultaneously . . . the . . .
- loop reactors can be used for the preparation of polyether carbonate polyols. These include, in general, reactors. These are tube reactors with recycling of substances, such as, for example, a jet loop reactor, which can also be operated continuously, or a loop of tube reactors. The use of a loop reactor is of advantage in particular because back-mixing can be realized here, so that the epoxide concentration should be low. In order to realize complete conversion, a tube (“dwell tube”) is often installed downstream.
- the polyether carbonate polyols obtained according to the invention have a functionality of at least 1, preferably of from 1 to 8, particularly preferably from 1 to 6 and very particularly preferably from 2 to 4.
- the molecular weight is preferably 400 to 20,000 g/mol and particularly preferably 500 to 10,000 g/mol.
- alkylene oxides having 2-24 carbon atoms can be employed for the process according to the invention.
- the alkylene oxides having 2-24 carbon atoms are, for example, one or more compounds chosen from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide, butadiene monoxide, isoprene
- H-functional starter substance Compounds with H atoms which are active for the alkoxylation can be employed as a suitable H-functional starter substance.
- Groups which have active H atoms and are active for the alkoxylation are, for example, —OH, —NH 2 (primary amines), —NH— (secondary amines), —SH, and —CO 2 H, and —OH and —NH 2 are preferred and —OH is particularly preferred.
- the H-functional starter substance employed is, for example, one or more compounds chosen from the group consisting of monofunctional alcohols, polyfunctional alcohols, polyfunctional amines, polyfunctional thiols, amino alcohols thioalcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polyethyleneimines, polyether-amines (e.g. so-called Jeffamine® from Huntsman, such as e.g. D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding products of BASF, such as e.g.
- polytetrahydrofurans e.g. PolyTHF® of BASF, such as e.g. PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800, 2000
- the C 1 -C 24 -alkyl fatty acid esters which contain on average at least 2 OH groups per molecule are commercial products such as Lupranol Balance® (BASF AG), Merginol® types (Hobum Oleochemicals GmbH), Sovermol® types (Cognis GmbH & Co. KG) and Soyol®TM types (USSC Co.).
- Monofunctional starter compounds which can be employed are alcohols, amines, thiols and carboxylic acids.
- Monofunctional alcohols which can be used are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3-
- amines Possible monofunctional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
- Monofunctional thiols which can be used are: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol.
- Monofunctional carboxylic acids which may be mentioned are: formic acid, acetic acid, propionic acid, butyric acid, fatty acids, such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
- Polyfunctional alcohols which are suitable as H-functional starter substances are, for example, difunctional alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, methylpentanediols (such as, for example, 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis-(hydroxymethyl)-cyclohexanes (such as, for example, 1,4-bis-(hydroxymethyl)cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, di
- the polyether polyols in particular behave in an advantageous manner in the activation.
- the H-functional starter substances can also be chosen from the substance class of polyether polyols, in particular those with a molecular weight Mn in the range of from 100 to 4,000 g/mol.
- Polyether polyols which are built up from recurring ethylene oxide and propylene oxide units are preferred, preferably with a content of from 35 to 100% of propylene oxide units, particularly preferably with a content of from 50 to 100% of propylene oxide units.
- These can be random copolymers, gradient copolymers or alternating or block copolymers of ethylene oxide and propylene oxide.
- Suitable polyether polyols built up from recurring propylene oxide and/or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex®, Baygal®, PET® and polyether polyols of Bayer MaterialScience AG (such as e.g. Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Polyether® S180).
- Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex®, Baygal®, PET® and polyether polyols of Bayer MaterialScience AG such as e.g. Desmophen® 3600Z, Desm
- suitable homo-polyethylene oxides are, for example, the Pluriol® E brands of BASF SE
- suitable homo-polypropylene oxides are, for example, the Pluriol® P brands of BASF SE
- suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, the Pluronic® PE or Pluriol® RPE brands of BASF SE.
- the H-functional starter substances can also be chosen from the substance class of polyester polyols, in particular those with a molecular weight Mn in the range of from 200 to 4,500 g/mol. At least difunctional polyesters are employed as polyester polyols. Polyester polyols preferably comprise alternating acid and alcohol units. Acid components which are employed are e.g. succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixture of the acids and/or anhydrides mentioned. Alcohol components which are used are e.g.
- polyester ether polyols which can likewise serve as starter substances for the preparation of the polyether carbonate polyols, are obtained.
- Polycarbonate diols can furthermore be employed as H-functional starter substances, in particular those with a molecular weight Mn in the range of from 150 to 4,500 g/mol, preferably 500 to 2,500, which are prepared, for example, by reaction of phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols.
- polycarbonates are to be found e.g. in EP-A 1359177.
- the Desmophen® C types of Bayer MaterialScience AG such as e.g. Desmophen® C 1100 or Desmophen® C 2200, can be used as polycarbonate diols.
- polyether carbonate polyols can be employed as H-functional starter substances.
- polyether carbonate polyols which are obtainable by the process according to the invention described here are employed.
- These polyether carbonate polyols employed as H-functional starter substances are prepared beforehand for this in a separate reaction step.
- the H-functional starter substances in general have a functionality (i.e. number of H atoms per molecule which are active for the polymerization) of from 1 to 8, preferably of 2 or 3.
- the H-functional starter substances are employed either individually or as a mixture of at least two H-functional starter substances.
- Preferred H-functional starter substances are alcohols of the general formula (IX) HO—(CH 2 ) x —OH (IX)
- x is a number from 1 to 20, preferably an even number from 2 to 20.
- alcohols according to formula (IV) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
- Further preferred H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols according to formula (IX) with ⁇ -caprolactone, e.g.
- H-functional starter substances which are furthermore preferably employed are water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols built up from recurring polyalkylene oxide units.
- the H-functional starter substances are particularly preferably one or more compounds chosen from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol is built up from a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide.
- the polyether polyols preferably have a molecular weight Mn in the range of from 62 to 4,500 g/mol and a functionality of from 2 to 3, and in particular a molecular weight Mn in the range of from 62 to 3,000 g/mol and a functionality of from 2 to 3.
- H-functional is understood as meaning the number of H atoms per molecule of the starter compound which are active for the alkoxylation.
- DMC catalysts for use in the homopolymerization of epoxides are known in principle from the prior art (see e.g. U.S. Pat. Nos. 3,404,109, 3,829,505, 3,941,849 and 5,158,922). DMC catalysts, which are described e.g. in U.S. Pat. No.
- EP-A 700 949 has a very high activity in the homopolymerization of epoxides and render possible the preparation of polyether polyols at very low catalyst concentrations (25 ppm or less), so that in general it is no longer necessary to separate off the catalyst from the finished product.
- the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complexing ligand (e.g. tert-butanol), also contain a polyether with a number-average molecular weight of greater than 500 g/mol, are a typical example.
- the DMC catalysts according to the invention are obtained by a procedure in which
- the double metal cyanide compounds contained in the DMC catalysts according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
- an aqueous solution of zinc chloride preferably in excess, based on the metal cyanide salt, such as, for example, potassium hexacyanocobaltate
- potassium hexacyanocobaltate is mixed and dimethoxyethane (glyme) or tert-butanol (preferably in excess, based on zinc hexacyanocobaltate) is then added to the suspension formed.
- Metal salts which are suitable for the preparation of the double metal cyanide compounds preferably have the general formula (X) M(X) n (X) wherein
- suitable metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, iron(III) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride and nickel(II) nitrate. Mixtures of various metal salts can also be employed.
- Metal cyanide salts which are suitable for the preparation of the double metal cyanide compounds preferably have the general formula (XIV) (Y) a M′(CN) b (A) c (XIV) wherein
- suitable metal cyanide salts are sodium hexacyanocobaltate(III), potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyanocobaltate(III).
- Preferred double metal cyanide compounds which the DMC catalysts according to the invention contain are compounds of the general formula (XV) M x [M′ x′ (CN) y ] z (XV),
- Suitable double metal cyanide compounds are zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III) and cobalt(II) hexacyanocobaltate(III). Further examples of suitable double metal cyanide compounds are to be found e.g. in U.S. Pat. No. 5,158,922 (column 8, lines 29-66). Zinc hexacyanocobaltate(III) is particularly preferably used.
- organic complexing ligands added in the preparation of the DMC catalysts are disclosed, for example, in U.S. Pat. No. 5,158,922 (see in particular column 6, lines 9 to 65), U.S. Pat. Nos. 3,404,109, 3,829,505, 3,941,849, EP-A 700 949, EP-A 761 708, JP 4 145 123, U.S. Pat. No. 5,470,813, EP-A 743 093 and WO-A 97/40086).
- water-soluble, organic compounds with hetero atoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound are employed as organic complexing ligands.
- Preferred organic complexing ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
- Particularly preferred organic complexing ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), and compounds which contain both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as e.g.
- Organic complexing ligands which are most preferred are chosen from one or more compounds of the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane-methanol.
- the aqueous solutions of the metal salt e.g. zinc chloride
- employed in a stoichiometric excess at least 50 mol %, based on the metal cyanide salt, that is to say at least a molar ratio of metal salt to metal cyanide salt of 2.25 to 1.00
- the metal cyanide salt e.g. potassium hexacyanocobaltate
- the organic complexing ligand e.g. tert-butanol
- a suspension which contains the double metal cyanide compound e.g. zinc hexacyanocobaltate
- the organic complexing ligand can be present in the aqueous solution of the metal salt and/or of the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound. It has proved to be advantageous to mix the aqueous solutions of the metal salt and of the metal cyanide salt and the organic complexing ligand with vigorous stirring.
- the suspension formed in the first step is then optionally treated with a further complexing component.
- the complexing component is preferably employed in a mixture with water and organic complexing ligand.
- a preferred method for carrying out the first step i.e. the preparation of the suspension
- is carried out employing a mixing nozzle, particularly preferably employing a jet disperser as described in WO-A 01/39883.
- the solid i.e. the precursor of the catalyst according to the invention
- the solid is isolated from the suspension by known techniques, such as centrifugation or filtration.
- the solid which has been isolated is subsequently washed with an aqueous solution of the organic complexing ligand (e.g. by resuspending and subsequent renewed isolation by filtration or centrifugation).
- an aqueous solution of the organic complexing ligand e.g. by resuspending and subsequent renewed isolation by filtration or centrifugation.
- water-soluble by-products such as potassium chloride
- the amount of organic complexing ligand in the aqueous washing solution is between 40 and 80 wt. %, based on the total solution.
- further complexing component is optionally added to the aqueous washing solution, preferably in the range of between 0.5 and 5 wt. %, based on the total solution.
- washing is carried out in a first washing step (iii-1) with an aqueous solution of the unsaturated alcohol (e.g. by resuspending and subsequent renewed isolation by filtration or centrifugation), in order to remove, for example, water-soluble by-products, such as potassium chloride, from the catalyst according to the invention in this manner.
- the amount of unsaturated alcohol in the aqueous washing solution is between 40 and 80 wt. %, based on the total solution of the first washing step.
- the first washing step is repeated once or several times, preferably once to three times . . .
- washing operation or preferably, a . . . will be . . . . It is preferable, however, to use a non-aqueous solution for further washing operations, e.g. a mixture or solution of unsaturated alcohol, of organic complexing ligand and further complexing components (preferably in the range of between 0.5 and 5 wt. %, based on the total amount of the washing solution of step (iii-2)), employed as the washing solution, and the solid . . . washed with this once or several times, preferably once to three times.
- a non-aqueous solution for further washing operations e.g. a mixture or solution of unsaturated alcohol, of organic complexing ligand and further complexing components (preferably in the range of between 0.5 and 5 wt. %, based on the total amount of the washing solution of step (iii-2)), employed as the washing solution, and the solid . . . washed with this once or several times, preferably once to three times.
- the solid which has been isolated and optionally washed is then dried, optionally after pulverization, at temperatures of in general 20-100° C. and under pressures of from in general 0.1 mbar to normal pressure (1013 mbar).
- the polyether carbonate polyols obtainable by the process according to the invention have a low content of by-products and can be processed without problems, in particular by reaction with di- and/or polyisocyanates, to give polyurethanes, in particular flexible polyurethane foams.
- polyether carbonate polyols which are based on an H-functional starter compound which has a functionality of at least 2 are preferably employed.
- the polyether carbonate polyols obtainable by the process according to the invention can furthermore be used in uses such as detergent and cleaning agent formulations, drilling liquids, fuel additives, ionic and nonionic surfactants, lubricants, process chemicals for papermaking or textile production or cosmetic formulations.
- polyether carbonate polyols to be used must comply with certain substance properties, such as, for example, molecular weight, viscosity, polydispersity, functionality and/or hydroxyl number.
- the weight- and number-average molecular weight of the polymers formed were determined by means of gel permeation chromatography (GPC). The procedure was in accordance with DIN 55672-1: “Gel permeation chromatography, Part 1-Tetrahydrofuran as the eluting agent”. Polystyrene samples of known molecular weight were used here for the calibration.
- OH number (hydroxyl number) was determined in accordance with DIN 53240-2, pyridine being used as the solvent, however, instead of THF/methylene chloride. Titration was carried out with 0.5 molar ethanolic KOH (end point detection by means of potentiometry). Castor oil with an OH number specified by certificate functioned as the test substance.
- the unit stated in “mg/g” relates to mg[KOH]/g[polyether carbonate polyol].
- the ratio of the substance amount of metal salt employed relative to the substance amount of cobalt employed, originating from the DMC catalyst, is also indicated.
- a weight content of Co of 11.0 wt. % is used for calculating the substance amount of cobalt originating from the DMC catalyst. This was determined by means of x-ray fluorescence analysis. On this basis, 141 mg of DMC catalyst employed (prepared according to Example 6 of WO-A 01/80994) contain a substance amount of cobalt of 0.26 mmol.
- the content of CO 2 incorporated in the resulting polyether carbonate polyol and the ratio of propylene carbonate to polyether carbonate polyol were determined by means of 1 H-NMR (Bruker, DPX 400, 400 MHz; pulse program zg30, waiting time d1: 10 s, 64 scans). The sample was dissolved in deuterated chloroform in each case.
- the factor 102 results from the sum of the molecular weights of CO 2 (molecular weight 44 g/mol) and that of propylene oxide (molecular weight 58 g/mol), the factor 58 results from the molecular weight of propylene oxide and the factor 146 results from the molecular weight of the starter employed, 1,8-octanediol.
- CC ′ A ⁇ ( 4.5 ) * 102 N * 100 ⁇ % ( XIX )
- the composition based on the polymer content (consisting of polyether polyol, which was built up from the starter and propylene oxide during the activation steps which took place under CO 2 -free conditions, and polyether carbonate polyol, built up from the starter, propylene oxide and carbon dioxide during the activation steps which took place in the presence of CO 2 and during the copolymerization), the non-polymer constituents of the reaction mixture (i.e. cyclic propylene carbonate and any unreacted propylene oxide present) were eliminated by calculation.
- CO 2 content in the polyether carbonate polyol stated (“CO 2 incorporated”; see the following examples and Table 1) is standardized to the content of the polyether carbonate polyol molecule which was formed during the copolymerization and, where appropriate, the activation steps in the presence of CO 2 (i.e. the content of the polyether carbonate polyol molecule which results from the starter (1,8-octanediol) and from the reaction of the starter with epoxide which was added under CO 2 -free conditions was not taken into account here).
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the additive A was first added here as a solution in the 25 g of PO [additive addition A2].
- the start-up of the reaction manifested itself by a temperature peak (“hot spot”) and by a drop in pressure to values close to the starting pressure (approx. 1 bar) [activation 1].
- 20 g of PO [activation 2] which contained the additive A where appropriate [additive addition A3]
- 19 g of PO, which contained the additive A where appropriate [additive addition A4] were metered in rapidly [activation 3], as a result of which in each case a temperature peak and a drop in pressure in turn occurred.
- the preparation was carried out in accordance with the general preparation instructions, 4-nitrophenol, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 4-nitrophenol, as the additive A, being dissolved in the amount of propylene oxide used for the activations 1, 2 and 3 and this solution being added accordingly in the activation steps [additive addition A2, A3, A4].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 4-tert-butyl-(pyro)catechol, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenothiazine, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenothiazine, as the additive A, being added in the amount of propylene oxide used for the activation 1 [additive addition A2].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenoxazine, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- TEMPO 2,2,6,6-tetramethylpiperidine 1-oxyl
- starter 1,8-octanediol
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, trans- ⁇ -nitrostyrene, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, ⁇ -methylstyrene, as the additive A, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- Examples 3-12 If the organic additives mentioned in Examples 3-12 are added, the time to the hot spot under carbon dioxide [activation 4] is sometimes shortened significantly, so that less time must be spent in carrying out the reaction. All the organic additives of Examples 3-12 improve the selectivity (cyclic/linear value decreases) and lead to polyether carbonate polyols with a low polydispersity. Advantageously, a higher incorporation of carbon dioxide into the polymer is also achieved with the additive phenoxazine (Example 9).
- the preparation was carried out in accordance with the general preparation instructions, calcium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, aluminium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenothiazine, as the additive A, and calcium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 2,4-dinitrophenol, as the additive A, and calcium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 4-nitrophenol, as the additive A, and calcium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenothiazine, as the additive A, and aluminium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 2,4-dinitrophenol, as the additive A, and aluminium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, 4-nitrophenol, as the additive A, and aluminium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenoxazine, as the additive A, and calcium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- the preparation was carried out in accordance with the general preparation instructions, phenoxazine, as the additive A, and aluminium stearate, as the metal salt B, being initially introduced into the reaction vessel together with the DMC catalyst and 1,8-octanediol (starter) as a solid [additive addition A1 and metal salt addition B1].
- the polyether carbonate polyol prepared in this way is distinguished by the following properties:
- OH number of the polyether carbonate polyol was 60.3 mg/g
- Polydispersity was 1.22.
- Examples 16 to 23 of Table 2 demonstrate the advantageous effect of the simultaneous use of an additive A) and a metal salt B). Compared with the process without these additives (Comparison Example 1, Table 1), a more favourable selectivity, a shorter activation time and at the same time a high content of CO 2 incorporated in the resulting polyether carbonate polyol are achieved.
- the combination of 4-nitrophenol or 2,4-dinitrophenol with calcium stearate or aluminium stearate (Examples 17, 18, 20 and 21) proved to be particularly favourable.
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Abstract
Description
- (α) the H-functional starter substance or a mixture of at least two H-functional starter substances is initially introduced into the reaction vessel and, where appropriate, water and/or other readily volatile compounds are removed by elevated temperature and/or reduced pressure (“drying”), the DMC catalyst being added to the H-functional starter substance or the mixture of at least two H-functional starter substances before or after the drying,
- (β) for the activation, a part amount (based on the total amount of the amount of alkylene oxides employed in the activation and copolymerization) of one or more alkylene oxides is added to the mixture resulting from step (α), it being possible for this addition of a part amount of alkylene oxide optionally to be carried out in the presence of CO2, and the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited, and it also being possible for step (β) to be carried out several times for the activation,
- (γ) one or more alkylene oxides and carbon dioxide are metered continuously into the mixture resulting from step (β) (“copolymerization”), it being possible for the alkylene oxides employed for the copolymerization to be identical to or different from the alkylene oxides employed in the activation,
- g=0, 1, 2, preferably 1 or 2, and
- Ri represents an amino, bromo, chloro, cyano, fluoro, iodo, methoxy, methyl or nitro group, preferably a nitro group.
- g has the above-mentioned meaning and
- Rj represents an acetamido, amino, bromo, n-butyl, iso-butyl, tert-butyl, chloro, cyano, ethoxy, ethyl, fluoro, iodo, methoxy, methyl, nitro, iso-propyl, n-propyl group.
- Preferably, the pyrocatechols are 4-tert-butyl-pyrocatechol.
- g and Rj have the above-mentioned meaning, and
- Rk represents an H or a C1-C20-alkyl group, preferably H or a methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, hexyl, cyclohexyl group.
- g has the above-mentioned meaning, and
- R1 represents an H, C1-C20-alkyl group (for example methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, hexyl, cyclohexyl group), acetamido, amino, bromo, chloro, cyano, ethoxy, ethyl, fluoro, hydroxyl, iodo, methoxy, nitro group. It is furthermore possible for the thiazole and/or the benzothiazole fragments to be linked to one another via disulfide bridges.
- g, Rk and Rj have the above-mentioned meaning, and
wherein in the case of the 1,4-oxazines according to the formula (VIa), these can also be the corresponding 1,2-oxazines and/or 1,3-oxazines, and the derivatives of 1,4-oxazine (formula (VIa)) are preferred.
- (α) the H-functional starter substance or a mixture of at least two H-functional starter substances is initially introduced into the reaction vessel and, where appropriate, water and/or other readily volatile compounds are removed by elevated temperature and/or reduced pressure (“drying”), the DMC catalyst being added to the H-functional starter substance or the mixture of at least two H-functional starter substances before or after the drying,
- (β) for the activation, a part amount (based on the total amount of the amount of alkylene oxides employed in the activation and copolymerization) of one or more alkylene oxides is added to the mixture resulting from step (α), it being possible for this addition of a part amount of alkylene oxide optionally to be carried out in the presence of CO2, and the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited, and it also being possible for step (β) to be carried out several times for the activation,
- (γ) one or more alkylene oxides and carbon dioxide are added to the mixture resulting from step (β) (“copolymerization”), it being possible for the alkylene oxides employed for the copolymerization to be identical to or different from the alkylene oxides employed in the activation,
R1—COO− (VII)
wherein R1 represents H, C1 to C30-alkyl (such as, for example, CH3, CH3—CH2, CH3—CH2—CH2, CH3—(CH2)3, CH3—(CH2)4, CH3—(CH2)5, CH3—(CH2)6, CH3—(CH2)7, CH3—(CH2)8, CH3—(CH2)14, CH3—(CH2)16 and branched isomers thereof), C7 to C30-alkaryl (such as, for example, benzyl) or C6 to C30-aryl (such as, for example, phenyl or naphthyl).
−OOC—R2—COO− (VIII)
wherein R2 represents a single bond (in the case of oxalate), C1 to C30-alkylene (such as, for example, CH2, CH2—CH2, (CH2)3, (CH2)4, (CH2)5, (CH2)6, (CH2)7, —CH═CH— (in the case of maleate or fumarate)), C7 to C30-alkaryl (such as, for example, benzyl) or C6 to C30-aryl (such as, for example, phenyl or naphthyl).
- (β1) in a first activation step a first part amount (based on the total amount of the amount of alkylene oxides employed in the activation and copolymerization) of one or more alkylene oxides is added to the mixture resulting from step (α), it being possible for this addition of the part amount of alkylene oxide optionally to be carried out in the presence of CO2, but preferably in the absence of CO2, and the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited,
- (β2) in a second activation step after the temperature peak reached in the preceding activation step, a second part amount (based on the total amount of the amount of alkylene oxides employed in the activation and copolymerization) of one or more alkylene oxides is added to the mixture resulting from the preceding activation step, it being possible for this addition of the part amount of alkylene oxide optionally to be carried out in the presence of CO2, but preferably in the absence of CO2, and the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited.
- (β3) optionally, in a third activation step or further activation steps, after the temperature peak reached in the preceding activation step, step (β2) is repeated zero to five times, preferably once to four times, particularly preferably exactly once, this addition of the part amount or these additions of the part amounts of alkylene oxide being carried out in the absence of CO2, and the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited,
- (β4) optionally, in a further activation step or further activation steps, after the temperature peak reached in the preceding activation step, step (β3) is repeated once to five times, preferably once to four times, particularly preferably exactly once, this addition of the part amount or these additions of the part amounts of alkylene oxide being carried out in the presence of CO2, and wherein the temperature peak (“hot spot”) which occurs due to the subsequent exothermic chemical reaction and/or a drop in pressure in the reactor then in each case being awaited.
HO—(CH2)x—OH (IX)
- (i) in the first step an aqueous solution of a metal salt is reacted with the aqueous solution of a metal cyanide salt in the presence of one or more organic complexing ligands, e.g. of an ether or alcohol,
- (ii) wherein in the second step the solid is separated off by known techniques (such as centrifugation or filtration) from the suspension obtained from (i),
- (iii) wherein, if appropriate, in a third step the solid which has been isolated is washed with an aqueous solution of an organic complexing ligand (e.g. by resuspending and subsequent renewed isolation by filtration or centrifugation),
- (iv) wherein the solid obtained, if appropriate after pulverization, is subsequently dried at temperatures of in general 20-120° C. and under pressures of from in general 0.1 mbar to normal pressure (1013 mbar),
and wherein in the first step or immediately after the precipitation of the double metal cyanide compound (second step), one or more organic complexing ligands, preferably in excess (based on the double metal cyanide compound), and optionally further complexing components are added.
M(X)n (X)
wherein
- M is chosen from the metal cations Zn2+, Fe2+, Ni2+, Mn2+, Co2+, Sr2+, Sn2+, Pb2+ and Cu2+, preferably M is Zn2+, Fe2+, Co2+ or Ni2+,
- X are one or more (i.e. different) anions, preferably an anion chosen from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
- n is 1 if X=sulfate, carbonate or oxalate and
- n is 2 if X=halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate,
or suitable metal salts have the general formula (XI)
Mr(X)3 (XI)
wherein - M is chosen from the metal cations Fe3+, Al3+, Co3+ and Cr3+,
- X are one or more (i.e. different) anions, preferably an anion chosen from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
- r is 2 if X=sulfate, carbonate or oxalate and
- r is 1 if X=halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate,
or suitable metal salts have the general formula (XII)
M(X)s (XII)
wherein - M is chosen from the metal cations Mo4+, V4+ and W4+
- X are one or more (i.e. different) anions, preferably an anion chosen from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
- s is 2 if X=sulfate, carbonate or oxalate and
- s is 4 if X=halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate,
or suitable metal salts have the general formula (XIII)
M(X)t (XIII)
wherein - M is chosen from the metal cations Mo6+ and W6+
- X are one or more (i.e. different) anions, preferably an anion chosen from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
- t is 3 if X=sulfate, carbonate or oxalate and
- t is 6 if X=halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate.
(Y)aM′(CN)b(A)c (XIV)
wherein
- M′ is chosen from one or more metal cations of the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), preferably M′ is one or more metal cations of the group consisting of Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II),
- Y is chosen from one or more metal cations of the group consisting of alkali metal (i.e. Li+, Na+, K+, Rb+) and alkaline earth metal (i.e. Be2+, Mg2+, Ca2+, Sr2+, Ba2+),
- A is chosen from one or more anions of the group consisting of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, azide, oxalate or nitrate and
- a, b and c are integers, wherein the values for a, b and c are chosen such that the metal cyanide salt has electroneutrality; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
Mx[M′x′(CN)y]z (XV),
- wherein M is as defined in formula (III) to (VI) and
- M′ is as defined in formula (VII), and
- x, x′, y and z are integers and are chosen such that the double metal cyanide compound has electroneutrality.
Preferably - x=3, x′=1, y=6 and z=2,
- M=Zn(II), Fe(II), Co(II) or Ni(II) and
- M′=Co(III), Fe(III), Cr(III) or Ir(III).
- cyclic carbonate (which was formed as a by-product) resonance at 4.5 ppm, carbonate, resulting from carbon dioxide incorporated in the polyether carbonate polyol (resonances at 5.1 to 4.8 ppm), unreacted PO with resonance at 2.4 ppm, polyether polyol (i.e. without incorporated carbon dioxide) with resonances at 1.2 to 1.0 ppm, the 1,8-octanediol incorporated as the starter molecule with a resonance at 1.6 to 1.52 ppm.
- A(4.5)=area of the resonance at 4.5 ppm for cyclic carbonate (corresponds to an H atom)
- A(5.1-4.8)=area of the resonance at 5.1-4.8 ppm for polyether carbonate polyol and an H atom for cyclic carbonate.
- A(2.4)=area of the resonance at 2.4 ppm for free, unreacted PO
- A(1.2-1.0)=area of the resonance at 1.2-1.0 ppm for polyether polyol
- A(1.6-1.52)=area of the resonance at 1.6 to 1.52 ppm for 1,8-octanediol (starter)
N=[A(5.1−4.8)−A(4.5)]*102+A(4.5)*102+A(2.4)*58+0.33*A(1.2−1.0)*58+0.25*A(1.6−1.52)*146 (XVIII)
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.9 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol=0.21;
- OH number of the polyether carbonate polyol was 67.2 mg/g;
- Polydispersity was 1.45.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.4 wt. %.
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol remained unchanged at 0.21 (i.e. as in Comparison Example 1).
- OH number of the polyether carbonate polyol was 69.1 mg/g;
- Polydispersity was poorer (1.65 instead of 1.45).
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.3 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.15;
- OH number of the polyether carbonate polyol was 61.3 mg/g;
- Polydispersity was 1.40
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 18.3 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.19;
- OH number of the polyether carbonate polyol was 65.5 mg/g;
- Polydispersity was 1.22
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 18.0 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.16;
- OH number of the polyether carbonate polyol was 59.3 mg/g;
- Polydispersity was 1.17
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.8 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.18;
- OH number of the polyether carbonate polyol was 65.1 mg/g;
- Polydispersity was 1.38
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 18.6 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.15;
- OH number of the polyether carbonate polyol was 57.8 mg/g;
- Polydispersity was 1.30
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 17.8 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.19;
- OH number of the polyether carbonate polyol was 64.9;
- Polydispersity was 1.19
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.8 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.17;
- OH number of the polyether carbonate polyol was 56.7 mg/g;
- Polydispersity was 1.40
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.0 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.16;
- OH number of the polyether carbonate polyol was 61.8 mg/g;
- Polydispersity was 1.23
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.5 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.15;
- OH number of the polyether carbonate polyol was 62.6 mg/g;
- Polydispersity was 1.42
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 19.0 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.18;
- OH number of the polyether carbonate polyol was 64.6 mg/g;
- Polydispersity was 1.17
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 17.2 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.22;
- OH number of the polyether carbonate polyol was 70.5 mg/g;
- Polydispersity was 1.47
Discussion of the Results Examples 1-13 (Table 1)
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.2 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.10;
- OH number of the polyether carbonate polyol was 64.3 mg/g;
- Polydispersity was 1.37.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 23.1 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.15;
- OH number of the polyether carbonate polyol was 63.3 mg/g;
- Polydispersity was 1.86.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.1 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.09;
- OH number of the polyether carbonate polyol was 65.5 mg/g;
- Polydispersity was 1.27.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.4 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.09;
- OH number of the polyether carbonate polyol was 63.2 mg/g;
- Polydispersity was 1.24.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 20.4 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.09;
- OH number of the polyether carbonate polyol was 63.7 mg/g;
- Polydispersity was 1.23.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 21.7 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.16;
- OH number of the polyether carbonate polyol was 66.9 mg/g;
- Polydispersity was 1.40.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 23.4 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.16;
- OH number of the polyether carbonate polyol was 66.5 mg/g;
- Polydispersity was 1.66.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 24.1 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.13;
- OH number of the polyether carbonate polyol was 61.5 mg/g;
- Polydispersity was 1.61.
- CO2 incorporated [wt. %], based on the part of the polymer formed under CO2: 18.3 wt. %;
- Selectivity stated as the ratio of cyclic carbonate (undesirable by-product) to polyether carbonate polyol was 0.13;
- OH number of the polyether carbonate polyol was 62.3 mg/g;
- Polydispersity was 1.24.
TABLE 1 |
Results of the polyether carbonate polyol preparation |
[mmol of | CO2 | ||||||
additive A)]/ | Time 1 | incorporation | Selectivity | OH number | Poly- | ||
Example | Additive A) | [mmol of Co] | [min] | [wt. %] | cyclic/linear | [mg of KOH/g] | dispersity |
1 (comp.) | without additive | 0 | 33 | 19.9 | 0.21 | 67.2 | 1.45 |
2 (comp.) | 2,4,6-tri-tert-butylphenol (31 g dissolved | 448.59 | 60 | 20.4 | 0.21 | 69.1 | 1.65 |
in 435 g of PO (continuous PO addition)) | |||||||
3 | 4-nitrophenol | 1.67 | 6 | 19.3 | 0.15 | 61.3 | 1.40 |
4 | 4-nitrophenol (dissolved in 64 g of PO, | 1.67 | 7 | 18.3 | 0.19 | 65.5 | 1.22 |
addition during activation) | |||||||
5 | 2,4-dinitrophenol | 1.67 | 14 | 18.0 | 0.16 | 59.3 | 1.17 |
6 | 4-tert-butyl-pyrocatechol | 1.67 | 17 | 19.8 | 0.18 | 65.1 | 1.38 |
7 | phenothiazine | 1.67 | 6 | 18.6 | 0.15 | 57.8 | 1.30 |
8 | phenothiazine (dissolved in 25 g of PO, | 1.67 | 7 | 17.8 | 0.19 | 64.9 | 1.19 |
addition in one activation step) | |||||||
9 | phenoxazine | 1.67 | 21 | 20.8 | 0.17 | 56.7 | 1.40 |
10 | 2,2,6,6-tetramethylpiperidine 1-oxyl | 1.67 | 15 | 19.0 | 0.16 | 61.8 | 1.23 |
11 | trans-β-nitrostyrene | 1.67 | 19 | 19.5 | 0.15 | 62.6 | 1.42 |
12 | 2,2′-dithiobis(benzothiazole) | 1.67 | 9 | 19.0 | 0.18 | 64.6 | 1.17 |
13 (comp.) | α-methylstyrene | 1.67 | 30 | 17.2 | 0.22 | 70.5 | 1.47 |
comp. = comparison example |
TABLE 2 |
Results of the polyether carbonate polyol preparation |
OH | |||||||||
[mmol of | [mmol of | CO2 | number | ||||||
additive A)]/ | metal salt B)]/ | Time 1 | incorporation | Selectivity | [mg of | Poly- | |||
Example | Additive A) | Metal salt B) | [mmol of Co] | [mmol of Co] | [min] | [wt. %] | cyclic/linear | KOH/g] | dispersity |
14 (comp.) | without additive A) | calcium stearate | 0 | 2.54 | 15 | 20.2 | 0.10 | 64.3 | 1.37 |
15 (comp.) | without additive A) | aluminium stearate | 0 | 1.67 | 19 | 23.1 | 0.15 | 63.3 | 1.86 |
16 | phenothiazine | calcium stearate | 1.67 | 2.54 | 7 | 20.1 | 0.09 | 65.5 | 1.27 |
17 | 2,4-dinitrophenol | calcium stearate | 1.67 | 2.54 | 7 | 20.4 | 0.09 | 63.2 | 1.24 |
18 | 4-nitrophenol | calcium stearate | 1.67 | 2.54 | 7 | 20.4 | 0.09 | 63.7 | 1.23 |
19 | phenothiazine | aluminium stearate | 1.67 | 1.67 | 10 | 21.7 | 0.16 | 66.9 | 1.40 |
20 | 2,4-dinitrophenol | aluminium stearate | 1.67 | 1.67 | 12 | 23.4 | 0.16 | 66.5 | 1.66 |
21 | 4-nitrophenol | aluminium stearate | 1.67 | 1.67 | 12 | 24.1 | 0.13 | 61.5 | 1.61 |
22 | phenoxazine | calcium stearate | 1.67 | 2.54 | 8 | 18.3 | 0.13 | 62.3 | 1.24 |
23 | phenoxazine | aluminium stearate | 1.67 | 1.67 | 8 | 19.8 | 0.18 | 60.9 | 1.22 |
comp. = comparison example |
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US11174348B2 (en) | 2016-11-11 | 2021-11-16 | Dow Global Technologies Llc | Polycarbonate based polyols |
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EP2658895B1 (en) * | 2010-12-27 | 2021-06-23 | Dow Global Technologies LLC | Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound |
EP2530101A1 (en) * | 2011-06-01 | 2012-12-05 | Bayer MaterialScience AG | Method for manufacturing polyether polyols |
EP2703425A1 (en) * | 2012-08-27 | 2014-03-05 | Bayer MaterialScience AG | Method for manufacturing polyether carbonate polyols |
EP2703426A1 (en) * | 2012-08-27 | 2014-03-05 | Bayer MaterialScience AG | Method for manufacturing polyether carbonate polyols |
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GB201515350D0 (en) | 2015-08-28 | 2015-10-14 | Econic Technologies Ltd | Method for preparing polyols |
EP3219741A1 (en) * | 2016-03-18 | 2017-09-20 | Covestro Deutschland AG | Method for manufacturing polyether carbonate polyols |
GB201703324D0 (en) | 2017-03-01 | 2017-04-12 | Econic Tech Ltd | Method for preparing polyether carbonates |
CN111201264A (en) * | 2017-10-18 | 2020-05-26 | 科思创德国股份有限公司 | Diblock copolymers and their use as surfactants |
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